Manufacture of products from aromatic amines and sulphur chloride



me n June 7,1927.

v um Eo sTATE s PATENT OFFICE.

JOSEPH v. Mares, or iron'rcnam, mew JERSEY, assrenoa, IBY' masxm ASSIGNMENTS, I To omEroN ELLIS, or mon'rcnarn, mew quasar.

MANUFACTURE OE.PRODUGTS-FBOM AROMATIG AMINES AND SULPHUR CHLORIDE.-

No Drawing.

I This invention relates I to a method of producing a reaction product of an aminoaromatic compound with sulphurchloride.

The invention is especially concerned with the production of the reaction of sulphur monoor di-chloride with amino compounds in a concentrated form, as for example in the form of concentrated solutlons or as the pure substances themselves. By the reaction of sulphur on the material in a concentrated state, bodies having improved solubility are obtainable.

- Amon the amino bodies which may be employed in carrying out the present process, simple amines such as aniline, toluidme, xylidine, benzidine and its derivatives, and the like may be mentioned aswell a complex mixtures of aminobodies produced by nitrating and reducing coal tar oils and residues, or mixtures, such as may be ob tained by the admixture of various simple or complex amino substances. More complicated amino compounds aresubstances such as phenylene diamine, the. amino phenols and cresols as anisidine and the amino compounds of naphthalene such as monoand dinaphthylami-ne. These substances 'may be treated directly with sulphur chloride or theygmay be reacted upon in solution. in a suitable solvent such forexample asben'zol, toluol, solvent naphtha, gasoline, carbon tetrachloride and the like. In a similar manner the sulphur chloride maybe introduced tion 0 products of t in the form of a solution in one of the solvents as mentioned or'an "other suitable solvent. Preferably'asin icated the reaction is brought about in highly concentrated solutions or with the commercially pure products themselves without dilution with any solvent. In place of the sul hur chlorides mentioned above,.sulphur an "chlorine may be caused toreact with these amino' compounds under suitable reacting conditions;

' The temperature at which the reaction takes lace is ofimportanoe' in the produce desired degree of solubility. The tendency-of higher temperatures is to produce substances which are soluble in oil or hydrocarbon solvents and to soirlrlie extent in alcohol while reaction at low te .eratures, generally speaking, produces ucts having greater s'olubility n water.

or example when" aniline is treated with sulphur chloride-in the cold' substantially Application filed May '10, me. Serial 110. 296,057.

the entire product. is soluble in acidulated water. The product produced in this manner appears to retain the basic qualities of aniline to a considerable extent at least and is fairly easily soluble in a dilute'solution of hydrochloric acid. The base itself is soluble in alcohol. On the other hand when the reaction is allowed to take placewithout any special control'of temperature, the combinatlon or change is very'violent, the mass 1 heats up rapidly and colored vapors are evolved. The product obtained in this man nor is much less soluble in acidulated water, scarcely more than 20 to 25% of the product going into aqueous acid solution uner these conditions.

The reaction may be effected b bringing the essential reagents together un er various conditions. A. substance such as aniline may for example be vaporized and the vapors assed into liquid sulphur chloride or rought in contact with the vapors of the latter. In this .casethe reaction may take place either at an elevated or at alow tern-- 'per'ature. For-example the vapors of aniline or naphthylamine may be passed into cold liquid sulphur chloride. On the. other hand the hot vapors of these amines maybe contacted with the hot vapors of sulphur chloride, in this case the reaction is noticeably violent and a product having a low degree of solubility in acidulated water is ob ta1ned.

Inlieu of treatment in the vapor form the.

amino compound such for example as aniline 1s added to liquid sulphur chloride or the latter, may be added to the liquid aniline.

In this case it is desirable to cool the aniline strongly and add the sulphur chloride very gradually stirring vigorously in order to distribute the chloride thoroughly through the aniline. When the. product is in a solld form such for example as naphthalamilie it may be powdered and sulphur chloride added thereto. In this case orlikewise the reac.--

tion mass may be strongly cooled to moderate' the violence of thejreactio'n or the naphthylamine may be extended by means of heating. Ordinarily however,

lutions diluted even more than that indicated but it is not desirable with the majority of amino compounds.

The product obtained frommany of the amino compounds is sometimes of a complex character and contains bodies of different solubilities. In some cases a portion may be soluble, in acidulated water, another portion in an aromatic hydrocarbon such as benzol v and a third portion in alcohol. The extracbenzol and alcohol and 'these it is preferable to extractfirst with tion with acidulated water yields a material which for the purposes of the present invention may be termed a water-soluble product. In some instances the residue after water extraction is not soluble in either benzol, alcohol or similar solvents and this residue may be useful as an insoluble material. On the other hand other reaction mixtures give 'as indicated, material soluble in benzol or in order to separate benzol and 'then with alcohol. By this method of successive extraction water-soluble, oil-soluble and spirit-soluble materials are obtained. I

As an illustration of a reaction yielding a As I soluble product the following may be given:

100 parts by volume ofaniline are kept cool by surrounding with ice or other suitable freezing mixture. Sulphur chloride is.

* of sulphur' monochloride. and

added very slowly with thorough agitation until 30. parts by volume of sulp ur chloride have been added to the aniline. The parts, by weight are about 2:1. The; resulting productis a deep violet colored solid material of the consistency of a thick paste. This product. is practically completely soluble in water containing. the requisite amount of acid. It is also soluble to the same extent in "alcoholic spirit.

As an example of the production of a;

roduct soluble a part of which is soluble ydrocarbon solvents such as benzol,'solvent naphtha,'gasoline, and the like, and another part of which 'is soluble in spirit (alcohol),

the followin is given:

20 parts weight-of alpha-naphthylamine are mailed and kept at as low a temperature as possible in the melted state. 4 parts by volume of a mixture of equal parts i toluene (1. e.

3.4 parts by weight of sulfur chloride and I 1.7 of toluene) are slowly added to the;-

melted naphthylamine. In this exampleabout 17 parts of sulphur chloride are used per 100 parts of the amino compound, which corresponds to about 6.4 mols. of alpha-.

naphthylamine to 1 mol. of sulphurmonochloride (figured as S Cl :135). The resulting mass is soluble in spirit (i. e. alco-.

hol), and possesses a deep violet color. The product is now given a further heating, this changes the violet material into a greenish product.v This green product "is composed of two materials, and in this case in substantially equal quantity one of which is soluble in hydrocarbon solvents such as benzol, solventnaphtha and the like and the other portion. is soluble'in alcohol.

As an example of the different course which the reaction takes when the amine compound is added to an excess of sul 'hur chloride as compared 4 with the pro ucts which are obtained when ride is added to an excess pound, the following example is given in the sulphur chlo- .which the amino compound is added to an excess of sulphur chloride, the amino comaniline. Add 80 parts by volume of aniline pound in this case being a liquid, namely,

of the aminocomto parts by-volume of sulphur chloride (about 1: 2 by weight) carrying out. the addition very slowly.- "At this point the reaction mass becomes a stiff paste which is tarry in appearance. Now add 4.0 parts more by volume of aniline in order to use up the excess of sulphur chloride. By extracting this reaction; mass with'for example 10% hydrochloric or sul huric acids it is found that about 60% of the mass is insoluble.

when

the followin is given; 1

Make a so ution of 20 parts by volume of xylidine in 15 parts by'volume of toluene, agitate thoroughly and add slowly by volume of sulphur monochloride. The

parts by weight would be about 4 1 or about 13:3 mols. Filter the resulting pasty anexample of'the results obtained sulphur chloride is added to a very concentrated solution of an amino compound 3 parts .action mass and extract with benzol, uponevaporation of the benzol the residue is a reddish-brown oil-soluble material. The

residue fromthe benzol, extraction. is "of a violet color, solublein methyl, ethyl, propyl and amyl alcohols. What I claim is dissolved in a solvent in the form of a concentrated. solution while maintaining the mixture 0001. v V

2. The rocess which com 'rises addin liquid sulpliur'chloride adua y toa cool body. of aniline,'said a ine being in the free state at the commencement-o1 the operation.

' 3. A- process which comprises "reacting.

upon afmixture of at least two volumes of 1. The process which consists in contact Y ing the sulphur chloride with anihn itself one volume of solvent, sulphur chloride, while preventin the reaction mg the reaction masscool, and continuing material is formed.

mixture from becoming hot, w ereby a solid the addition of sulphur chloride until not substantially less than 1 mol. of the latter 4. A process which comprises reacting e b en addedwith sulphur chloride upon a free simple A P e whleh comprlsesi slowly addamino aromatic compound, while the latter g s p ur hl ride o a cold material conis in a free state and while in the form of a taining an aminoderivatiye of an aromatic solution of at least 66% strength at the behy r n, Whlle kecplng' he reaction ginning of the operation. mass cool. and cont nuing the addition of 5 A b hich comprises l l ddsulphur chloride until not substantially being sulphur chloride to a cold material con- 10W 3 molsof the latter are added'PeP 1 taining about 6.4 mols. of an amino deriva- -fi' he amine- .tive of an' aromatic hydrocarbon, while keep- JOSEPH V. MEIGS. 

